The processing of silver halide photographic materials, such as a silver halide color photographic material, comprises a color-developing process and a desilvering process. In the desilvering process, developed silver produced in the color-developing process is oxidized (bleached) to a silver salt by a bleaching agent having an oxidation action, and it is removed from the photosensitive layers after it is changed together with unused silver halide into a soluble silver ions by a fixing agent (fixing). As the bleaching agent, a ferric(III) ion complex salt (e.g., an aminopolycarboxylic acid/ferric(III) complex salt) is mainly used, and as the fixing agent, a thiosulfate is generally used.
The bleaching and the fixing are carried out in some cases separately in a bleaching step and a fixing step, and in some cases they are carried out simultaneously in a bleach-fix step. Details of these processing steps are described by James in The Theory of Photographic Process, 4th edition (1977).
The above processing steps are generally carried out by an automatic processor. Particularly, in recent years, rapid-processing service for customers is spreading through the installation of small-sized automatic processors called mini-labs in shops. A bleaching agent and a fixing agent are used in one and the same bath, which acts as a bleach-fix bath in the processing of color paper; this enables an automatic processor to be small and makes the rapid processing.
Further, in order to save resources and to preserve the environment, low-replenishment-rate measures are being taken positively. However, if low-replenishment-rate measures for a developer are taken simply, the accumulation of substances dissolved from the photographic material, particularly iodide ions and bromide ions, which are strong development inhibitors, lowers the development activity, leading to the problem that the rapidness is spoiled. For the purpose of reducing the accumulation of iodide ions and bromide ions and for attaining a rapid process, methods wherein a silver halide photographic material high in silver chloride content is used, which methods are disclosed in JP-A ("JP-A" means unexamined published Japanese patent application) Nos. 95345/1983, 232342/1984, and 70552/1986 and WO 87-04534 are considered to be effective means that makes possible rapid processing under low-replenishment-rate of a developer. Other methods for rapid processing, in which the pH of a developer or the processing temperature is elevated are also known.
JP-A No. 443/1992 discloses a process that allows the storage stability of a color image to be excellent. It makes low-replenishment-rate possible, and it permits the process to be carried out ultra-rapidly by processing a silver halide photographic material high in silver halide content with a color developer containing, as a dolor-developing agent, a hydroxyalkyl-substituted p-phenylenediamine derivative having a specific structure.
Concerning a washing step or a stabilizing step, JP-A Nos. 214155/1991 and 233452/1991 disclose processes that make possible low-replenishment-rate by a multi-stage countercurrent system and/or by reusing water that has been treated with a reverse osmosis membrane.
Thus, low-replenishment-rate is attempted in every processing step and it has become an important subject in recent years. It is known that, if the amount of washing water is reduced, the concentrations of iron salts and other salts in the washing bath increase and they remain on the photographic material, leading to the defect that the dye image deteriorates after long storage. However, the image quality of the processed sample is good and the defect is not fatal.
On the other hand, there is increased demand for higher image quality of color papers, and JP-A No. 177542/1984 discloses, as a method for enhancing sharpness, a method for improving sharpness of a photographic image by providing a hydrophilic colloid layer containing a white pigment on a paper support covered with synthetic resin film, to suppress the scattering of light on the support at the time of exposure.
However, when the above solid-dispersed substance was used in a high-silver-chloride photographic material that allowed rapid processing in order to improve sharpness of an image, first it became apparent that the fluctuation of the photographic sensitivity during the processing, due to a change of the processing conditions, increased. That is, when the processing was carried out at a higher processing temperature range, in order to perform a development process rapidly, a problem arose that the fluctuation of the photographic sensitivity during the processing, due to a change in temperature, increased.
Secondly, it was found that, when color development was effected with running solution with the replenishment rate being low and particularly when a washing step was also carried out with the replenishment rate being low, stain (coloring) was liable to occur on the processed image.
Thus, it is strongly desired to attain a processing method wherein the conventional high sharpness of an image is retained, the fluctuation of processing due to rapid processing is low, and/or an image with low stain is provided, even if the process is carried out with the replenishment rate being low.
The occurrence of stain referred herein will be further described. In the processing of a color photographic material, for the purpose of making the processing rapid with the replenishment rate being low and for making the processing simple, for example, if the running process is effected with the replenishment rate being low in the color-developing step, components dissolved from the photographic material and development-exhausted components accumulate considerably. Accordingly, substances produced during the development or produced due to the exhaustion with time become apt to be taken into the photographic material. The more lowered the replenishment rate of the succeeding washing step or the succeeding stabilizing step is, the more difficult it becomes to remove the above undesired substances. Similarly, in the case of the low-replenishment-rate of a bleach-fix bath, removal of the undesired substances becomes difficult.
Thus, when all the processing steps are carried out with the replenishment rate lowered, deterioration of the white background of the image, due to undesired substances remaining in the photographic material, becomes apparent. Especially, when a low-replenishment-rate running solution of a color developer is used, the occurrence of stain is a serious problem, and when the processing steps are carried out rapidly, stain on an image is liable to occur.
It is also found that, when inorganic substances, particularly such as colloidal silver and titanium oxide, are present densely, stain is liable to occur. The term "stain" used herein refers to coloring of a white background part, caused by coloring components in exhaustion accumulated components of a developing agent and the like, remaining in the processed photographic material.